JP3192659B2 - Pyrazolin-3,5-dione-containing compositions for dyeing keratin fibers; use in dyeing as couplers; dyeing method - Google Patents

Abstract

The present invention relates to a composition for dyeing keratin fibers, in particular human hair, containing, in a medium which is suitable for dyeing:as coupler, at least one compound of formula:or one of the addition salts thereof with an acid;and at least one oxidation base.

Description

The present invention relates to a composition for oxidative dyeing of keratin fibers such as hair, which contains at least one pyrazoline-3,5-dione compound as a coupler and contains at least one oxidation base. contains.

Using dye compositions comprising oxidation dye precursors, commonly referred to as oxidation bases, such as especially ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds, such as hair It is known to dye keratin fibers. Oxidation Dye The substance, the oxidation base, is a colorless or slightly colored compound which, when combined with the oxidation product, produces a colored compound which is dyed by an oxidative condensation process.

The shades obtained using these oxidation bases (shade
s) is a coupler or color modifi
ers), the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as indole compounds.

A wide range of colors is provided by the versatile molecules used as oxidation bases and couplers.

The so-called "permanent" coloration obtained by means of such oxidation dyes must further fulfill certain requirements. Then, toxic (toxicologica
l) must not have the drawbacks, the shade must be obtained at the desired intensity, and must exhibit excellent resistance to external factors (light, bad weather, washing, permanent waving, sweat, rubbing) .

Also, the dye must be able to coat the gray hair and, finally, must be as non-specific as possible, i.e. it was actually made otherwise sensitive between tip and root (ie damage Along the length of the same keratinous fiber (under the same conditions).

Applicants have discovered that by using a pyrazoline-3,5-dione compound as a coupler in the presence of an oxidation base, a novel, powerful, non-specific and especially It has been found that a dye having excellent resistance can be obtained.

 This observation forms the basis of the present invention.

The subject of the invention is, in a medium suitable for dyeing,-as a coupler at least one pyrazoline-3,5-dione compound of the formula (I) or an addition salt with an acid: In the above formula: R ₂ is a hydrogen atom; a halogen atom such as bromine, chlorine or fluorine; an acetylamide group; an alkoxy group (for example, methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, 2-cyano) Ethoxy, phenethyloxy, p-chlorobenzyloxy, methoxyethylcarbamoylmethoxy); aryloxy groups (for example, phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methane) Sulfonylphenoxy, 3-methylphenoxy, 1-naphthyloxy); acyloxy groups (eg, acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyalkyloxy, pyruviroyl) Oxy, cinnamoyloxy, myristoyloxy); arylthio groups (for example, phenylthio, 4
-Carboxyphenylthio, 2-ethoxy-5-tert-
Butylphenylthio, 2-carboxyphenylthio, 4
-Methanesulfonylphenylthio); alkylthio group (for example, methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio, 2- (diethylamino) ethylthio, ethoxyethylthio, phenoxyethylthio); heteroarylthio group (For example, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio); heteroaryloxy group (for example, 5-phenyl-2,3,4,5-tetrazolyloxy, -Benzothiazolyloxy); thiocyano group; N, N-diethylthiocarbonylthio group; dodecyloxythiocarbonylthio group; benzesulfonamide group; N-ethyltoluenesulfonamide group; pentafluorobutanamide group; , 4,5,6-pentafluorobenzamide group; p-cyanophenylurei Group (p-cyanopheny
lureido radical); N, N-diethylsulfamoylamino group; pyrazolyl group; imidazolyl group;
Triazolyl group; tetrazolyl group; benzimidazolyl group; 1-benzyl-5-ethoxy-3-hydantoinyl group; 1-benzyl-3-hydantoinyl group; 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; Oxy-
A group NR ^III R ^{IV comprising a} 1,2-dihydro-1-pyridyl group; an alkyl amide; an aryl amide; R ^III and R ^IV , wherein R ^III and R ^IV are the same or different. at best, C ₁ -C ₄ alkyl, it represents a hydroxyalkyl; indicating the or alkoxyalkyl carboxyl group; carboxyl and R ₁ and R ₃ is a hydrogen atom; a linear or branched C ₁ -
C ₅ alkyl group; C ₂ -C ₄ mono- - or polyhydroxyalkyl radical; C ₂ -C ₄ aminoalkyl radical; a phenyl group; a halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy,
A phenyl group substituted by a nitro, trifluoromethyl, amino or C ₁ -C ₄ alkylamino group; a benzyl group;
A benzyl group substituted by a halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, methylenedioxy or amino group; or In the above formula, m and n are the same or different integers in the range of 1 to 3, X represents an oxygen atom or an NH group, Y represents a hydrogen atom or a methyl group, and Z represents a methyl group, an OR group. or NRR 'represents a group, R and R' may be different even in the same, hydrogen atom, a methyl group or an ethyl group; an amino group; C ₁ -C ₄ alkylamino; carboxyl group; An alkoxycarbonyl group; an aryloxycarbonyl group; a 5- or 6-heterocycle having at least one nitrogen, sulfur or oxygen atom (eg, pyridyl, quinolyl, pyrrolyl, morpholyl, furyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl , Imidazolyl, thiadiazolyl); acyl group; sulfonyl group; phosphonyl group; R ₂ and R ₃ are water simultaneously R ₁ is other than a hydrogen atom, a C ₁ -C ₆ alkyl group or a phenyl group, if it represents an elementary atom; and-characterized in that it contains at least one oxidation base, A composition for dyeing such human keratin fibers.

Addition salts with acids for the compounds according to the invention can be chosen in particular from hydrochlorides, hydrobromides, tartrates, toluenesulphonates, benzenesulphonates, sulphates, lactates and acetates.

In the group R ₂ of the above formula (I), preferred groups are a hydrogen atom; C ₁ -C ₄ alkoxy; phenoxy;
₁ -C ₄ alkyl, carboxyl, phenoxy substituted with a trifluoromethyl group; an acyloxy group; benzyloxy; C ₁ -C ₄ alkylthio; phenylthio; hydrogen atom, C
A group with a R ^III and R ^IV NR ^III R ^IV,; _{the 1} -C ₄ alkyl, carboxyl, trifluoromethyl phenylthio substituted with a methyl group; C ₁ -C ₄ alkylamido; phenylamide
R ^III and R ^IV may be the same or different and represent C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl; carboxyl; from the group consisting of C ₁ -C ₄ alkoxycarboxyl groups Selected.

In the group R ₂ of Formula (I), particularly preferred groups are hydrogen; chlorine or bromine; methoxy or ethoxy; phenoxy; 4-methylphenoxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4
-Methylphenylthio; 2-tert-butylphenylthio;
Acetamide; phenylacetamide; dimethylamino; diethylamino; ethylmethylamino; (β-hydroxyethyl) methylamino.

Particularly preferred radicals R ₂ are hydrogen; is selected from the group consisting of dimethylamino; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamide.

In groups R ₁ and R ₃ of formula (I) above, preferred groups are hydrogen; C ₁ -C ₄ alkyl (eg, methyl, ethyl, isopropyl, t-butyl, n-propyl); C ₂ -C ₄ mono −
Or polyhydroxyalkyl (2-hydroxyethyl, 3,4-dihydroxybutyl); C ₂ -C ₄ aminoalkyl (eg, 2-aminoethyl); dialkylaminoalkyl (eg, 2- (N, N-dimethylamino) Ethyl); phenyl; phenyl substituted with a chlorine atom or methoxy, nitro, trifluoromethyl, amino, methylamino or methyl group; benzyl; benzyl substituted with chlorine, methoxy or methyl; alkoxycarbonyl (eg, methoxycarbonyl, Ethoxycarbonyl); aryloxycarbonyl (eg, phenyloxycarbonyl); pyridyl; furyl; thienyl; pyrrolyl; thiazolyl; acyl (eg, acetyl, 2-ethylcarbonyl).

Among the R ₁ and R ₃ groups, particularly preferred groups are hydrogen; methyl; ethyl; isopropyl; 2-hydroxyethyl; 2-aminoethyl; phenyl; 2-, 3- or 4-chlorophenyl; 3- or 4-methoxyphenyl Benzyl; 3- or 4-toluyl; methoxycarbonyl; ethoxycarbonyl; pyridyl; pyrazolyl;

Further, preferred groups R ₁ and R ₃ are selected from the group consisting of hydrogen; methyl; ethyl; isopropyl; phenyl; 4-chlorophenyl; 4-toluyl; benzyl; pyridyl;

Particularly preferred compounds of formula (I) are those wherein R ₁ represents hydrogen, methyl, ethyl or phenyl; R ₂ represents chlorine or ethoxy; R ₃ represents methyl, ethyl or phenyl.

As the compounds of the above formula (I), in particular, -1,2-diphenylpyrazolin-3,5-dione, -1,2-diethylpyrazolin-3,5-dione, -1,2-dimethylpyrazolin-3 , 5-dione, -4-chloro-1,2-diethylpyrazolin-3,5-dione, and addition salts of the above compounds with acids.

Synthetic intermediates and methods for the preparation of pyrazoline-3,5-dione compounds of the present invention are described in patents and patent applications.
JP 07-036159, JP 07-084348 and US Pat. No. 4,128,425, and the following publications: L. Wyzgowska, Acta. Pol. Pharm. 1982, 39 (1-3), 8
3-E. Hannig, Pharmazie, 1980, 35 (4), 231-MHElnagdi, Bull. Chem. Soc. Jap., 46 (6), 1830, 1
973-G. Cardillo, Gazz. Chim. Ital. 1966, 95, (8-9), 9
73.

The compound of the formula (I) is preferably present in an amount of 0.0005 to 12% by weight, more preferably 0.1% by weight, based on the total weight of the dye composition.
005 to 6% by weight.

The nature of the oxidation base that can be used in the dye compositions according to the invention is not critical. Such oxidation bases are preferably para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol,
Ortho-aminophenol and heterocyclic bases (hetero
cyclic bases), and acid addition salts of the compounds.

Examples of the para-phenylenediamine that can be used as an oxidation base in the dye composition according to the present invention include:
Compounds corresponding to the following formula (II) and addition salts with acids: In the above formula, R ⁵ is a hydrogen atom, C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl or (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄₎ ) Represents an alkyl group, R ₆ represents a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl group, and R ₇ represents a hydrogen atom, a chlorine atom A halogen atom such as C ₁ −
C ₄ indicated alkyl, sulfo, carboxyl, C ₁ -C ₄ mono-hydroxyalkyl or C ₁ -C ₄ hydroxyalkoxy radical, R ₈ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, and a .

In above-mentioned formula (II), when R ₇ is other than hydrogen atom, R ₅ and R ₆ are hydrogen atoms, and preferably R ₇ is R ₈ are the same, R ₇ is a halogen atom In some cases, it is preferred that R ₅ , R ₆ and R ₈ are hydrogen atoms.

As the para-phenylenediamine of the above formula (II),
In particular, para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-
Phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis (β-hydroxyethyl) -para-phenylenediamine, 4-amino-1- (β-methoxyethyl) aminobenzene and 2-chloro-para-phenylene Diamines, and addition salts of the above compounds with acids can be mentioned.

Bis (phenyl) alkylenediamines which can be used as oxidation bases in the dye compositions according to the invention include, in particular, compounds corresponding to the following formula (III) and addition salts with acids: In the above formula, Q ₁ and Q ₂ may be the same or different, and represent a group NHR _{12 in} which a hydroxyl group or R ₁₂ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, R ₉ represents a hydrogen atom or a C ₁ -C ₄ alkyl, C ₁ -C ₄ mono-hydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl or an amino group substituted by C ₁ may be -C ₄ aminoalkyl group, R ₁₀ and R ₁₁ may be the same or different and represent hydrogen or a halogen atom or a C ₁ -C ₄ alkyl group; A group obtained from the group consisting of: wherein n is an integer of 0 or more and 8 or less, and m is 0
And an integer of 4 or more.

As the bis (phenyl) alkylenediamine of the above formula (III), in particular, N, N′-bis (β-hydroxyethyl-N, N′-bis- (4′-aminophenyl) -1,3-diamino- 2-propanol, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl)
Tetramethylenediamine, N, N'-bis (β-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine and N, N'-bis (ethyl) -N, N'-bis (4'-amino-3'-methylphenyl) ethylenediamine, and addition salts of the above compounds with acids.

As the bis (phenyl) alkylenediamine of the formula (III), N, N′-bis (β-hydroxyethyl) -N, N ′
-Bis (4'-aminophenyl) -1,3-diaminopropanol or an addition salt of the above compound with an acid is preferred.

As the para-aminophenol used as the oxidation base in the dye composition according to the present invention, there may be mentioned, in particular, compounds corresponding to the following formula (IV) and addition salts with acids.

In the above formula, R ₁₃ is a hydrogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl or C ₁ -C ₄ amino R ₁₄ represents hydrogen or a fluorine atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ monohydroxyalkyl, C ₂ -C ₄ polyhydroxyalkyl, C ₁ -C ₄ aminoalkyl, cyano (C ₁ −
A C ₄ ) alkyl or (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkyl group, and at least one of the groups R _{13 and} R ₁₄ represents a hydrogen atom.

As the para-aminophenol of the above formula (IV), in particular, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol, 4-amino −
2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol and 4-amino-2- (β-hydroxyethylaminomethyl) phenol And addition salts of the above compounds with acids.

The ortho-aminophenol used as the oxidation base in the dye composition according to the present invention is particularly preferably 2-
Aminophenol, 2-amino-1-hydroxy-5-
Mention may be made of methylbenzene, 2-amino-1-hydroxy-6-methylbenzene and 5-acetamido-2-aminophenol, and addition salts of the above compounds with acids.

As the heterocyclic base used as the oxidation base in the dye composition according to the present invention, in particular, a pyridine derivative,
Pyrimidine derivatives and pyrazole derivatives, and addition salts with acids can be mentioned.

Pyridine derivatives include, for example, GB1026978 and 115, such as addition salts with 2,5-diaminopyridine and acids.
Particular mention may be made of the compounds described in 3196.

Pyrimidine derivatives include, for example, German Patent DE2359399 or Japanese Patent, such as 2,4,5,6-tetraaminopyrimidine and 4-hydroxy-2,5,6-triaminopyrimidine, and addition salts with acids. JP88-169571 and JP9
Particular mention may be made of the compounds described in 1-3333495.

Pyrazole derivatives include 4,5-diamino-1-methylpyrazole and 3,4-diaminopyrazole, and 1- (4′-chlorobenzyl) -4,5-diaminopyrazole and addition salts with acids, DE3843892 and D
E4133957 and International Patent Applications WO94 / 08969 and WO94 / 089
Particular mention may be made of the compounds described under 70.

According to the invention, the oxidation base is preferably from about 0.0005 to 12% by weight, based on the total weight of the dye composition, and is preferably from about 0.5% to about 0.5%.
More preferably, it is 005 to 6% by weight.

The dye compositions according to the invention can be used in addition to the compounds of the formula (I) and / or one or more direct dyes in order to change the shade obtained using an oxidized base or to give the shade a gloss. , One or more additional couplers.

The additional couplers which can be used in the composition according to the invention can be selected from couplers which can be used conventionally for oxidation dyeing, in particular meta-phenylenediamine, meta-aminophenol, meta- Mention may be made of diphenols, and heterocyclic couplers such as, for example, indole derivatives, indoline derivatives and the like, and addition salts of the compounds with acids.

These couplers include, among others, 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 3-aminophenol, 1,3
-Dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyloxy) benzene, 2-amino-4- ( β-hydroxyethylamino) -1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxyindole, 4- It can be selected from hydroxyindole, 4-hydroxy-N-methylindole and 6-hydroxyindoline, and addition salts of the above compounds with acids.

When these compounds are present, these additional couplers will add about 0.0005 to the total weight of the dye composition.
It is preferably from 5 to 5% by weight, more preferably from 0.005 to 3% by weight.

Oxidation base used in the dye composition of the present invention and / or
Alternatively, the addition salt of the additional coupler with an acid is chosen, in particular, from the hydrochloride, hydrobromide, sulfate, tartrate, lactate and acetate salts.

In general, a suitable medium (or support) for staining is
It consists of a mixture of water and at least one organic solvent in order to dissolve water or compounds which are not sufficiently soluble in water. As the organic solvent, for example, C ₁ -C ₄ lower alcohols such as ethanol and isopropanol; Kuriseroru; 2-butoxyethanol, propylene glycol,
Mention may be made of glycols and glycol ethers such as propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, and aromatic alcohols such as benzyl alcohol or phenoxyethanol, similar products and mixtures thereof.

The solvent is preferably present in a proportion of about 1 to 40% by weight, more preferably 5 to 30% by weight, based on the total weight of the dye composition.

The pH of the dye composition according to the invention is generally between 3 and 12. The desired value can be adjusted with acidifying or basifying agents commonly used for dyeing keratin fibers.

Acidifying agents can include, for example, carboxylic acids such as hydrochloric acid, orthophosphoric acid, tartaric acid, citric acid and lactic acid, and inorganic or organic acids such as sulfonic acid.

Examples of the basifying agent include aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and compounds of the following formula (V): Wherein R is a propylene residue optionally substituted with a hydroxyl group or a C ₁ -C ₄ alkyl group; R ₁₅ , R ₁₆ , R ₁₇ and R
₁₈ may be the same or different and includes a hydrogen atom or a C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl group.

The dye composition according to the present invention comprises anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, positive, nonionic, amphoteric or zwitterionic polymers or these. Mixtures of inorganic or organic thickeners, antioxidants, penetrants, sequestering agents,
Various adjuvants conventionally used in hair coloring compositions may be included, such as fragrances, buffers, dispersants such as silicones, film formers, preservatives and conditioners such as opacifiers.

Of course, those skilled in the art will recognize that the beneficial properties inherent in the dye compositions of the present invention are not adversely affected or substantially not adversely affected by the foreseen additives. In particular, attention will be paid to the selection of any auxiliary compounds mentioned above.

The dye composition according to the invention can be in various forms, such as liquid, creamy or gel, or any other form suitable for dyeing keratin fibers, especially hair.

A subject of the invention is also the use of pyrazoline-3,5-diones of the above formula (I) in combination as at least one oxidation base for the oxidative dyeing of keratin fibers, in particular human keratin fibers, including hair. It is used as a coupler.

Another subject of the invention is a method for the oxidative dyeing of keratin fibers, such as human keratin fibers, in particular with hair, using the dye compositions described above.

According to this method, at least one of the above dye compositions is applied to the fiber and, at acidic, neutral or alkaline pH, is added to the dye composition only at the time of use or separately or simultaneously or sequentially applied Color development is performed using an oxidizing agent present in the oxidizing composition.

According to a particularly preferred embodiment of the dye composition according to the invention, the dye composition is used in use with an oxidizing composition comprising at least one oxidizing agent present in a medium suitable for dyeing in an amount sufficient for color development. Mixed. The resulting mixture is applied to keratin fibres, for about 3-50 minutes, preferably about 5-5 minutes.
Leave for 30 minutes, after which the fibers are rinsed, washed with shampoo, rinsed again and dried.

The oxidizing agent present in the oxidizing composition described above is selected from oxidizing agents conventionally used for oxidative dyeing of keratin fibers, including hydrogen peroxide, urea peroxide, alkali metal bromides and perboric acid and persulfate. Such peracid group salts can be mentioned. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the above oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers is preferably in the range of about 3 to 12, more preferably 5 to 12. ~ 11. It is commonly used for dyeing keratin fibers and is adjusted to the desired value with an acidifying or basifying agent as described above.

The oxidizing composition is conventionally used in hair coloring compositions and may also include various adjuvants, as described above.

The final composition applied to the keratin fibers is liquid,
It can be in various forms, such as cream or gel, or any other form suitable for dyeing keratin fibers, especially hair.

Another subject of the invention is a dyeing "kit" or a multi-compartment device or any other multi-compartment containment system, the first containing the dye composition and the second containing the oxidizing composition. Composition.

These devices include a patent FR-2586913 in the name of the Applicant.
Means can be provided for delivering the desired mixture to the hair, such as the device described in.

( ^* ) Ordinary dye support:-2.0 g of benzyl alcohol-3.0 g of polyethylene glycol containing 6 mol of ethylene oxide-20.0 g of ethanol-buffered with ammonium citrate, commercially available from SEPPIC under the name Oramix CG110 6.0 g of aqueous (C ₈ -C ₁₀ ) alkyl polyglucoside containing 60% active substance 10.0 g of aqueous ammonia containing 20% NH ₃ 10.0 g of sodium metabisulphite
e) 0.228 g - when sequestrants suitable amount used, each dye composition, the same weight 6x10 ^-3 mol%
With an aqueous solution of ammonium persulfate.

90% of the resulting mixture at a rate of 10 g / g of hair
Was applied for 30 minutes to a chunk of natural gray hair with or without permanent waving, including white hair. After rinsing, washing with a standard shampoo and drying, the front and back masses were dyed in the shades summarized in the table below.

────────────────────────────────────────────────── ─── Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) A61K ^7/ 00-7/50 CA (STN) REGISTRY (STN)

Claims (23)

(57) [Claims] In a medium suitable for dyeing: at least one pyrazoline-3,5-dione compound of the formula (I) or an addition salt with an acid as a coupler: In the above formula: R ₂ is hydrogen atom; halogen atom such as bromine, chlorine or fluorine; acetylamide group; alkoxy group; acyloxy group; aryloxy group; arylthio group; alkylthio group; heteroarylthio group; Thiocyano group; N, N-diethylthiocarbonylthio group; dodecyloxythiocarbonylthio group; benzenesulfonamide group; N-ethyltoluenesulfonamide group;
Pentafluorobutanamide group; 2,3,4,5,6-pentafluorobenzamide group; p-cyanophenylureido group; N, N
Pyrazolyl group; imidazolyl group; triazolyl group; tetrazolyl group; benzimidazolyl group; 1-benzyl-5-ethoxy-3-hydantoinyl group; 1-benzyl-3-hydantoinyl group;
Group NR ^III R with 5,5-dimethyl-2,4-dioxo-3-oxazolidinyl; 2-oxy-1,2-dihydro-1-pyridyl group; alkylamide; arylamide; R ^III and R ^{IV IV} , wherein R ^III and R ^IV may be the same or different and represent C ₁ -C ₄ alkyl, hydroxyalkyl; carboxyl; or alkoxycarboxyl; R ₁ and R ₃ is a hydrogen atom; linear or branched C _1-
C ₅ alkyl group; C ₂ -C ₄ mono- or polyhydroxyalkyl group; C ₂ -C ₄ aminoalkyl group; phenyl group; halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy,
A phenyl group substituted by a nitro, trifluoromethyl, amino or C ₁ -C ₄ alkylamino group; a benzyl group;
A benzyl group substituted with a halogen atom or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, methylenedioxy or amino group; or In the above formula, m and n are integers, which may be the same or different in the range of 1 to 3,
X represents an oxygen atom or an NH group; Y represents a hydrogen atom or a methyl group; and Z represents a methyl group, an OR group or an NRR 'group, and R and R' may be the same or different; hydrogen atom, a methyl group or an ethyl group; an amino group; C ₁ -C ₄ alkylamino; carboxyl group; alkoxycarbonyl groups; aryloxycarbonyl group; at least one nitrogen, 5- or with sulfur or oxygen atom 6 A heterocyclic ring; an acyl group; a sulfonyl group; a phosphonyl group; when R ₂ and R ₃ simultaneously represent a hydrogen atom, R ₁ is other than a hydrogen atom, a C ₁ -C ₅ alkyl group or a phenyl group; A composition for dyeing keratin fibers, in particular human keratin fibers such as hair, characterized in that it contains at least one oxidation base. 2. The radicals R ₃ and R _{1 of the} formula (I) are hydrogen; C ₁ -C ₄
Alkyl; C ₂ -C ₄ mono- - or polyhydroxy alkyl;
C ₂ -C ₄ aminoalkyl; phenyl; dialkylaminoalkyl; chlorine, methoxy, nitro, trifluoromethyl, amino, phenyl substituted with methyl amino or methyl; benzyl; chlorine, benzyl substituted by methoxy or methyl; alkoxy The composition according to claim 1, wherein the composition is selected from the group consisting of carbonyl; aryloxycarbonyl; pyridyl; furyl; thienyl; pyrrolyl; thiazolyl and acyl. 3. The group R ₁ and R ₃ are hydrogen; methyl; ethyl;
Isopropyl; 2-hydroxyethyl; 2-aminoethyl;
Phenyl; 2-, 3- or 4-chlorophenyl; 3- or 4-methoxyphenyl; 3- or 4-toluyl; benzyl; methoxycarbonyl; ethoxycarbonyl; pyridyl; pyrazolyl and pyrrolyl. The composition according to claim 2, wherein 4. The group R ₁ and R ₃ are hydrogen; methyl; ethyl;
4. The composition according to claim 2, wherein the composition is selected from the group consisting of isopropyl; phenyl; 4-chlorophenyl; 4-toluyl; benzyl; pyridyl and pyrazolyl. 5. A compound of the formula (I) wherein R ₂ is hydrogen; C ₁ -C ₄ alkoxy; phenoxy; phenoxy substituted by hydrogen, C ₁ -C ₄ alkyl, carboxyl or trifluoromethyl; group; and R ^III; benzyloxy; C ₁ -C ₄ alkylthio; phenylthio; hydrogen atom, C ₁ -C ₄ alkyl, carboxyl, phenylthio substituted with a trifluoromethyl group; C ₁ -C ₄ alkylamido; phenylamide R
A group NR ^III R ^IV with an ^IV, R ^III and R ^IV is selected or different and the same, C ₁ -C ₄ alkyl, showing a C ₁ -C ₄ hydroxyalkyl; carboxyl and C characterized in that it is selected from the group consisting of ₁ -C ₄ alkoxy carboxyl group, a composition according to any one of claims 1 to 4. 6. The radical R ₂ of the formula (I) is hydrogen; chlorine or bromine; methoxy or ethoxy; phenoxy; 4-methylphenoxy; acyloxy; benzyloxy; methylthio or ethylthio; phenylthio; 4-methylphenylthio; Tert-butylphenylthio; acetamido; ferracetamide; dimethylamino; diethylamino; ethylmethylamino and (β-hydroxyethyl) methylamino,
A composition according to claim 5. 7. The method of claim 6, wherein the group R ₂ of formula (I) is selected from the group consisting of hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamide and dimethylamino. Composition. 8. A compound of formula (I) wherein:-R ₁ represents hydrogen, methyl, ethyl or phenyl;-R ₂ represents chlorine or ethoxy;-R ₃ represents methyl, ethyl or phenyl. The composition according to claim 1, wherein the composition is selected. 9. A compound of the formula (I) comprising: -1,2-diphenylpyrazolin-3,5-dione; -1,2-diethylpyrazolin-3,5-dione; 9. The composition of claim 8, wherein the compound is selected from zoline-3,5-dione, 4-chloro-1,2-diethylpyrazolin-3,5-dione, and an addition salt of the compound with an acid. Composition. 10. An addition salt of a compound of the formula (I) with an acid is selected from hydrochloride, hydrobromide, sulfate, tartrate, benzenesulfonate, lactate, tosylate and acetate. A composition according to any one of the preceding claims. 11. The composition according to claim 1, wherein the at least one compound of formula (I) represents 0.0005 to 12% by weight of the total weight of the dye composition. 12. The composition according to claim 1, wherein the compound of formula (I) represents 0.0005 to 12% by weight of the total weight of the dye composition.
The composition of claim 11. 13. The method according to claim 1, wherein the oxidation base is selected from para-phenylenediamine, bis (phenyl) alkylenediamine, para-aminophenol, ortho-aminophenol and heterocyclic bases, and addition salts of the compounds with acids. 13. The composition according to claim 1, wherein the composition is characterized in that: 14. The oxidation base is present in an amount of 0.1% of the total weight of the dye composition.
14. The composition according to claim 1, wherein the composition represents from about 0005 to 12% by weight. 15. The oxidation base is present in an amount of 0.1% of the total weight of the dye composition.
15. The composition according to claim 14, wherein the composition represents from 005 to 6% by weight. 16. The method according to claim 1, which comprises, in addition to the compound of the formula (I), one or more additional couplers and / or one or more direct dyes. A composition as described. 17. A medium (or support) suitable for dyeing,
Water or water and lower C ₁ -C ₄ alcohol, and glycerol, glycols and glycol ethers, aromatic alcohols, characterized in that it consists of at least one organic solvent selected from similar products and mixtures thereof,
A composition according to any one of claims 1 to 16. 18. The composition according to claim 1, wherein the pH is between 3 and 12. 19. The method according to claim 1, which is in liquid, creamy or gel-like form or in another form suitable for dyeing keratin fibers such as hair. A composition according to claim 1. 20. A compound of formula (I) as claimed in claim 1 or 10 as a coupler in a composition for the oxidative dyeing of keratin fibres, such as human keratin fibres, especially including hair. Use of an addition salt with an acid in combination with at least one oxidation base. 21. The at least one dye composition according to any one of claims 1 to 19, which is applied to keratin fibers such as human keratin fibers including hair, and is added to the dye composition only at the time of use. The method for oxidatively dyeing keratin fibers, wherein the color is developed at an acidic, neutral, or alkaline pH using an oxidizing agent present in an oxidizing composition which is applied separately or simultaneously or sequentially. 22. The method according to claim 21, wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromides and peracid salts such as perboric acid and persulfuric acid. . 23. A multi-section dyeing "kit" or multi-section apparatus wherein the first section contains the dye composition of any one of claims 1 to 19 and the second section contains the oxidizing composition.